Herein, we report for the first time, the high regio- and enantioselective ring opening of a biobased itaconic anhydride catalyzed by the Pseudomonas cepacia lipase (PCL) in tert-butylmethylether (TBME) at room temperature. This approach is easy, efficient, eco-friendly and afforded in one-step a series of a highly valuable monoesters itaconates (achiral or enantioenriched) using various alcohols as nucleophiles with 100% atom economy. In all cases the β-monoester isomer was the predominant product of the reaction. Using achiral primary alcohols as substrates, a variety of novel itaconates were obtained in moderate to excellent yields (50 - 90%). For select examples, product characterization was carried out using X-ray diffraction, in addition to standard techniques. The application of this approach was performed for the preparation of enantioenriched 4-monoester itaconates via enzymatic kinetic resolution.